Magnetic Phase Transitions in Substituted Spinels of Zn1−x Cu χ Cr2 Se4; 0.0 ≤ x ≤ 0.3

Magnetic and crystallographic properties have been studied by neutron powder diffraction and measurements of magnetization and magnetization hysteresis-loops for substituted spinels of Zn_1?xCu_xCr₂Se₄ with 0.0≤x≤0.3. It is found that the Zn_0.85Cu_0.15Cr₂Se₄ spinel has two magnetic phase transitions at 23.0 K (Néel temperature; T _N) and 410 K (Curie temperature; T _C) and that the Zn_0.70Cu_0.30Cr₂Se₄ spinel has magnetic transitions at 24.5 K (T _N) and 415 K (T _C) on heating. The low-temperature magnetic phase transition is from a spiral antiferromagnet to a ferromagnet, and the high-temperature magnetic phase transition is from a ferromagnet to a paramagnet, while ZnCr₂Se₄ shows a magnetic phase transition only from a spiral antiferromagnet to a paramagnet at about 21.0 K. From neutron powder diffraction, it is also found that the spinels of Zn_1?x Cu _x Cr₂Se₄; 0.0 ≤ x ≤ 0.3. show satellite-like magnetic reflection having indexes (h ± Q, k, l) with Q = 0.470 below T _N and short-range order of spins (spin glass-like) above T _N. The incommensurate antiferromagnetic phase below T _N results from a spiral long-range order of the spins of Cr³⁺. The intermediate ferromagnetic phase between T _N and T _C is related not to the spiral spin order but to double-exchange magnetic interaction among Cr³⁺ and Cr⁴⁺ mediated by current carriers, positive holes, which is made by the substitution of Zn²⁺ ions with Cu¹⁺ ions in Zn_1?x Cu _x Cr₂Se₄.     

Suppression of the spin-glass state by indirect exchange via charge carriers in spinellides xCuCr2Se4-(1−x)Cu0.5Me0.5Cr2Se4 (Me = Ga,In)

Spin glass (SG) is observed in semiconducting solid solutions xCuCr₂Se₄-(1?x)Cu_0.5Me_0.5Cr₂Se₄ (Me = In, Ga) for 0?x?0.1. For x0.1 the material exhibits p-type metal conductivity. For x?0.6 the magnetic properties are purely ferromagnetic (FM), while for 0.1 <x?0.2 an unusual mixed two-phase SG+FM state is found. Indirect exchange via charge carriers is assumed to be responsible for SG suppression.     

High resolution neutron scattering study of low-energy magnetic excitations in Nd2-xCexCuO4

The low-energy magnetic excitations (?ω ≤ 2 meV) of polycrystalline samples of Nd_2-xCe_xCuO₄ with x = 0, 0.1 and 0.15 have been measured with high resolution inelastic neutron scattering using time-of-flight technique at temperatures below 0.3 K. All observed scattering originates from transitions within the ground state doublet of Nd³⁺. For Nd₂CuO₄ the response is inelastic, and shows at least three different modes, of which one is almost dispersionless. For x = 0.1 the excitation spectrum shifts towards lower energies, but the main features of the undoped compound are still visible, whereas for x = 0.15 the response is mainly quasi-elastic but remains localised in Q-space around the first magnetic Bragg point (0.5 0.5 1). A comparison with data obtained on a triple-axis-spectrometer on single crystals with x = 0.0 and x = 0.15 reveals that the response of the doped sample in the [0 0 1] direction is still inelastic.     

Helimagnetism of CuxZn1−xCr2Se4 (for 0.0 ≤ × ≤ 0.1)

Abstract

The magnetization, the susceptibility and the magnetic anisotropy field of Cu _x Zn_1?xCr₂Se₄ compounds have been studied at low temperatures (down to 2.9 K) in: high magnetic stationary fields (up to 14 T), high pulsed magnetic fields (up to 25 T), medium magnetic stationary fields (up to 0.6 T). The magnetic structure of these spinels was studied by neutron powder diffraction.

The magnetic properties of Cu_xZn_1?xCr₂Se₄ are explained in terms of the molecular field approximation assuming the existence of 90° exchange interactions, ferromagnetic for Cr-Se-Cr between the nearest Cr ions and antiferromagnetic for Cr-Se-Se-Cr between the second-nearest Cr ions. The exchange parameters and integrals for the whole series under consideration are calculated. Taking into account the three magnetic phase transitions observed in these spinels (Juszczyk, Krok, Okońska-Koz?owska, Broda, Warczewski, Byszewski, 1981) and the neutron diffraction studies a modification of the simple spin spiral forced by a strong magnetic field is described.     

Preparation,stoichiometry and magnetic properties of Cu y Cr2Se4−z Br x spinels with 0.5≲x≲2

The chemical composition of Cu _y Cr₂Se_4?z Br _x spinels depends strongly on the preparation parameters. Spinels with 0.8?y?1.2, 0.5?x?2, and 0?z?x?0.2 have been prepared. Whereas the lattice constanta _o of these spinels differs only by less than approximately 0.6%, their Curie temperatureT _c depends sensitively on the spinel composition. For Cu_1.1Cr₂Se_3.4Br_o.46,a _o=1.0410 nm andT _c=310 K were found to compared witha ₀=1.0447 nm andT _c=84 K of CuCr₂Se₂Br₂.     

Formation of ceramic solid solutions in a SrTiO<Subscript>3</Subscript>-BiScO<Subscript>3</Subscript> system

X-ray structural, X-ray phase, and dilatometric analyses were used to explore specific features of the formation of solid solutions in the (1 − x)SrTiO₃−xBiScO₃ system with x = 0.0, 0.1, 0.2, 0.3, 0.4, and 0.5. It was found that the synthesis of solid solutions from the initial Bi₂O₃, Sc₂O₃, TiO₂, and SrCO₃ components is accompanied by a considerable increase in the linear dimensions of the samples, depending on their composition. Solid solutions with x > 0.1 are formed through intermediate phases (Sr₅Bi₆O₁₄ at x = 0.2; Sr_0.78Bi_2.22O₄ at x = 0.3; and Sr_2.25Bi_6.75O_12.38 at x = 0.4 and 0.5). It was shown that the samples with x = 0.2, 0.3, 0.4, and 0.5 have two phases: one with a cubic Pm3m structure and one with a tetragonal I4/mcm structure.     

Susceptibility of the paraprocess in spinel ferrites with a frustrated magnetic structure

The temperature dependence of the susceptibility of the paraprocess χ_para (T) is investigated for samples in the CuGa_xAl_xFe_2?2xO₄ (x = 0.2, 0.3, 0.4, 0.5, 0.6, 0.7), CuGa_xAl_2xFe_2?3xO4 (x = 0.1, 0.2, 0.3, 0.4, 0.5), and Ga_xFe_{1? x}NiCrO₄ (x = 0.0, 0.2, 0.4, 0.6, 0.8) systems. It is found that long-range magnetic order arises in spinel ferrites at the temperature T_tran of the transition from a cluster spin-glass state to a frustrated magnetic structure with a maximum in the temperature dependence of the susceptibility of the paraprocess.     

Negative chemical pressure effects induced by Y substitution for Ca on the ‘exotic’ magnetic behavior of the spin-chain compound, Ca3Co2O6

The magnetic behavior of a solid solution, Ca_{3 x} Y_x CO₂ O₆, based on the ‘exotic’ spin-chain compound, Ca₃Co₂O₆, crystallizing in K₄CdCl₆-derived rhombohedral structure is investigated. Among the compositions investigated(x = 0.0, 0.3, 0.5, 0.75 and 1.0), single-phase formation persists up tox = 0.75, with the elongation of the c-axis. The present investigations reveal that the temperature at which the ‘so-called’ ‘partially disordered antiferromagnetic structure’ sets in (which occurs at 24 K for the parent compound,x = 0.0) undergoes gradual reduction with the substitution of Y for Ca, attaining the value of about 2.2 K for the nominalx = 1.0. The trend observed in this characteristic temperature is opposite to that reported under external pressure, thereby establishing that Y substitution exerts negative chemical pressure. Anomalous steps observed in the isothermal magnetization at very low temperatures (around 2 K) forx = 0.0, which have been proposed to arise from ‘quantum tunneling effects’ are found to vanish by a small substitution (x = 0.3) of Y for Ca. Systematics in AC and DC magnetic susceptibility behavior with Y substitution for Ca have also been probed. We believe that the present results involving the expansion of chain length without disrupting the magnetic chain may be useful to the overall understanding of the novel magnetism of the parent compound.     

Jahn-Teller distortion and magnetoresistance in electron doped Sr1-xCexMnO3 (x = 0.1, 0.2, 0.3 and 0.4)

Neutron and electron diffraction, electrical transport and magnetic measurements have been carried out on a newly synthesized electron doped Sr_1-xCe _x MnO₃ (x = 0.1, 0.2, 0.3 and 0.4) system. For x=0.1, while cooling, it undergoes a first-order metal-insulator transition at 315 K which is associated with a structural transition from cubic (Pm3m) to tetragonal (I4/mcm) due to Jahn-Teller ordering () which stabilizes a chain like (C-type) antiferromagnetic ground state with . The antiferromagnetic insulator state is insensitive to an applied magnetic field of 7 T. With increase of x, while the nuclear structure at room temperature for x=0.2 and 0.3 remains tetragonal, for x=0.4 it becomes orthorhombic (Imma) where the doping electrons seem to occupy mainly the d _x2-y2 symmetry. Further, the JT distortion and the antiferromagnetic interactions decrease with doping and a small negative magnetoresistance appears for . Magnetic measurements show that the dilution of antiferromagnetic interaction results into a spin glass like behaviour at low temperature for the samples with x=0.3 and 0.4. This behaviour is in contrast with the CMR properties of calcium based electron doped systems and hole doped manganites. The stability of C-type antiferromagnetic ordering in the electron doped system with large A-site cationic size may be responsible for the absence of double exchange ferromagnetism and CMR effect. Received 10 September 1999     

Microstructural and magnetic properties of Pr–BiCo co-substituted M-type Sr–Ca hexaferrites

We have synthesized the Pr–BiCo substituted hexaferrites with compositions of Sr_0.8-xCa_0.2Pr_xFe_12.0-x(Bi_0.5Co_0.5)_xO₁₉ (0.0?≤?x?≤?0.5) by the standard ceramic method. Results of X-ray diffraction analysis exhibits that the synthesized hexaferrites with x from 0.0 to 0.3 are in single magetoplumbite structure, and impurity phases are observed when x?≥?0.4. The surface morphology of magnets shows that hexaferrite grains have a hexagonal platelet shape with clear grain boundaries. The remanence first increases with x from 0.0 to 0.1, and then decreases when x?≥?0.1. The intrinsic coercivity decreases with x from 0.0 to 0.1, and then increases when x?≥?0.1. With x from 0.0 to 0.4, the changing trend of magnetic induction coercivity is in agreement with that of H_cj, while at x?≥?0.4, H_cb decreases. The maximum energy product initially increases with x from 0.0 to 0.2, and then decreases when x?≥?0.2.     

Effect of Cd on the structural, magnetic and electrical properties of nanostructured Mn-Zn ferrite

Nanoparticles of Mn_0.5Zn_0.5−xCd_xFe₂O₄ (x=0.0, 0.1, 0.2 and 0.3) have been synthesized by a chemical co-precipitation method. The lattice constant increases with increasing Cd content. X-ray calculations indicate that there is deviation in the cation distribution in the nanostructured spinel ferrite. The dielectric constant and dielectric loss decrease for the samples with Cd content up to x=0.2. However the dielectric constant rises for x=0.3. This is due to an increase in the hopping process at the octahedral (B sites). The dielectric constant increases with increase in temperature, indicating a thermally activated hopping process. The DC resistivity increases with Cd content up to x=0.2 and decreases for Cd content x=0.3. The maximum magnetization of all the samples decreases with increase in Cd content.     

Structural and magnetic properties of Pr3(Fe1−xCox)27.5Ti1.5 (x=0.0, 0.1, 0.2, 0.3)

A novel class of Co-substituted 3 : 29 materials, Pr₃(Fe_1−xCo_x)_27.5Ti_1.5 (x=0, 0.1, 0.2, 0.3) have been synthesized. Rietveld analysis of X-ray powder diffraction patterns for the x=0, 0.1 and 0.2 compositions showed that nearly all of the compounds are formed in monoclinic symmetry, with A2/m space group with traces of α-Fe, whereas, in x=0.3, additional traces of a (Co/Fe)–Ti (1 : 12) phase are also seen. The saturation magnetization increases with Co concentration both at 5 and 300 K and is explained on the basis of a rigid band model. A magnetic transition is observed for x=0.1 near 240 K. A large increase in Curie temperature, of about 180 K for x=0.1 and about 110 K for the other concentrations, is discussed on the basis of the strengthening of TM–TM exchange by the preferential occupation of Co in some of the Fe sites originally participating in antiferromagnetic bonds.     

Investigating the structure and dielectric properties of ceramic solid solutions of the SrTiO3-BiScO3 system

Ceramic samples of (1 − x)SrTiO₃-(x)BiScO₃ system with x = 0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5 were synthesized. Neither of the end members of this system are ferroelectric materials. X-ray diffraction analysis reveals that at room temperature, the samples with x = 0.2, 0.3, 0.4, and 0.5 consisted of a mixture of two phases: a cubic center-symmetric Pm3m phase and a tetragonal polar P4mm phase. Dielectric permittivity and dielectric losses measurements of these compositions showed anomalies associated with the diffuse phase transition characteristic of ferroelectrics.     

Doping effect of Mn on the magnetic behavior in Ni-Zn ferrite nanoparticles prepared by sol-gel auto-combustion

The ferrite samples of a chemical formula Ni_0.5−xMn_xZn_0.5Fe₂O₄ (where x=0.0, 0.1, 0.2, 0.3, 0.4, and 0.5) were synthesized by sol-gel auto-combustion method. The synthesized samples were annealed at 600 °C for 4 h. An analysis of X-ray diffraction patterns reveals the formation of single phase cubic spinel structure. The lattice parameter increases linearly with increase in Mn content x. An initial increase followed by a subsequent decrease in saturation magnetization with increase in Mn content is observed showing inverse trend of coercivity (H_c). Curie temperature decreases with increase in Mn content x. The initial permeability is observed to increase with increase in Mn content up to x=0.3 followed by a decrease, the maximum value being 362. Possible explanation for the observed structural, magnetic, and changes of permeability behavior with various Mn content are discussed.     

Reflectivity of Sn(Se1-xSx)2 mixed crystals

Reflectivity measurements in fundamental absorption range (3.6–13 eV) have been made on Sn(Se_1-xS_x)₂ mixed compounds for several compositions (x = 0.0, 0.1, 0.3, 0.5, 0.7, 0.9, 1.0). The composition dependence of the energy location of the reflectivity structures is found to be non-linear and different according to the electronic transitions involved. This behaviour is discussed in terms of electronic structure evolution related to the anion substitution.     

Effect of cation distribution on the structural and magnetic properties of nickel substituted nanosized Mn–Zn ferrites prepared by co-precipitation method

Nano particles of Mn_(0.5–x)Ni_xZn_0.5Fe₂O₄ (x=0.0, 0.1, 0.2, 0.3) have been synthesized by chemical co-precipitation method. The lattice constant and distribution of cation in the tetrahedral and octahedral sites have been deduced through X-ray diffraction (XRD) data analysis. The lattice constant (Å) for all Mn/Ni concentration is found to be less than that for the corresponding bulk values. X-ray intensity calculations indicate that there is deviation in the normal cation distribution. Magnetization decreases with increasing Ni concentration except for x=0.3, where it shows increasing trend. This is due to migration of Fe³⁺ ions from B-site to A-site, which reduces the B–B coupling and there by the spin canting in the B sublattice. The Curie temperature was found to decrease with increase in nickel concentration except for x=0.3, where it shows a rise. Coercivity is very low and is found to be inversely proportional to the grain size.     

Structural and magnetic properties of zinc- and aluminum-substituted cobalt ferrite prepared by co-precipitation method

Spinal ferrites having the general formula Co_{1 − x} Zn _x Fe_{2 − x} Al _x O₄ (x = 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6) were prepared using the wet chemical co-operation technique. The samples were annealed at 800°C for 12 h and were studied by means of X-ray diffraction, magnetization and low field AC susceptibility measurements. The X-ray analysis showed that all the samples had single-phase cubic spinel structure. The variation of lattice constant with Zn and Al concentration deviates from Vegard’s law. The saturation magnetization σ _s and magneton number n _B measured at 300 K using high field hysteresis loop technique decreases with increasing x, suggesting decrease in ferrimagnetic behaviour. Curie temperature T _C deduced from AC susceptibility data decreases with x, suggesting a decrease in ferrimagnetic behaviour.      

Phase diagram and oxygen annealing effect of FeTe1−xSex iron-based superconductor

Phase diagrams of as-grown and O₂-annealed FeTe_1?xSe_x determined from magnetic susceptibility measurement were obtained. For as-grown samples, the antiferromagnetic order was fully suppressed in the range region x≥0.15, and weak superconductivity appeared when x≥0.1. Beginning at x=0.5, weak superconductivity was found to evolve into bulk superconductivity. Interestingly, for O₂-annealed samples, complete suppression of magnetic order and the occurrence of bulk superconductivity were observed when x≥0.1. We found that O₂-annealing induces bulk superconductivity for FeTe_1?xSe_x. Oxygen probably plays a key role in the suppression of the magnetic order and the appearance of bulk superconductivity.     

Mössbauer and magnetic study of Mn2+- and Cr3+-substituted spinel magnesioferrites of the composition Mg1−xMnxFe2−2xCr2xO4

Chromium and manganese co-substituted spinel magnesioferrites of the composition Mg_1?x Mn _x Fe_2?2x Cr_2x O₄ (x?=?0.0, 0.1, 0.2, 0.3, and 0.5) were investigated with X-ray diffraction (XRD), Mössbauer spectroscopy and magnetic measurements. The cation distribution inferred suggests that Mn²⁺ and Cr³⁺ ions dominantly occupy the A- and B-sites respectively. The gradual decrease of the hyperfine fields and Curie temperatures with increasing x reflects a gradual weakening in the AB exchange interaction. Mössbauer data of the sample with x = 0.5 is suggestive of cation clustering and/or superparamagnetism. The magnetization data is suggestive of Yafet-Kittel-type canted magnetism.     

Comparing the physical properties of Pr/Gd and Pr/Ce substitutions in Ru(Gd<Subscript>1.5</Subscript>Ce<Subscript>0.5</Subscript>)Sr<Subscript>2</Subscript>Cu<Subscript>2</Subscript>O<Subscript>10−<Emphasis Type="Italic">δ</Emphasis></Subscript>

We have compared the electrical and magnetic properties of Ru(Gd_1.5−x Pr _x )Ce_0.5Sr₂Cu₂O_10−δ (Pr/Gd samples) with x = 0.0, 0.01, 0.03, 0.033, 0.035, 0.04, 0.05, 0.06, 0.1 and RuGd_1.5(Ce_0.5−x Pr _x ) Sr₂ Cu₂O_10−δ (Pr/Ce samples) with x = 0.0, 0.01, 0.03, 0.05, 0.08, 0.1, 0.15, 0.2 prepared by the standard solid-state reaction technique. We obtained the XRD patterns for different samples with various x. The lattice parameters versus x for different substitutions have been obtained from Rietveld analysis. To determine how the magnetic and superconducting properties of these layered cuprate systems can be affected by Pr substitution, the resistivity, and magnetoresistivity, with H _ext varying from 0.0 to 15 kOe, have been measured at various temperatures. Superconducting transition temperature T _c and magnetic transition T _irr , have been obtained through resistivity and ac susceptibility measurements. The T _c suppression due to Pr/Gd and Pr/Ce substitutions show competition between pair breaking by magnetic impurities, hole doping due to different valances of ions, difference in ionic radii, and oxygen stoichiometry. Pr/Gd substitution suppresses superconductivity more rapidly than for Pr/Ce, showing that the effect of hole doping and magnetic impurity pair breaking is stronger than the difference in ionic radii. In Pr/Gd substitution, the small difference between the ionic radii of Pr^3+,4+ and Gd³⁺, and absorption of more oxygen due to the higher valence of Pr with respect to Gd, decreases the mean Ru-Ru distance, and as a result, the magnetic exchange interaction becomes stronger with the increase of x. However, Pr/Ce substitution has the opposite effect. The magnetic parameters such as H _c , obtained through magnetization measurements versus applied magnetic field isotherm at 77 K and room temperatures, become stronger with x in Pr/Gd and weaker with x in Pr/Ce substitution.